Interface properties of nano-silica/thermotropic liquid crystalline polyesters (TLCP) composites were investigated by X-ray diffraction analysis and differential scanning calorimetory. The crystallinity of TLCP in the composites drastically decreased with an increase of nano-silica content, depending on the surface area of the silica particles. Little size effects (40 - 400 nm) in the particles and strong interaction between silica surface and the C=O moieties of TLCP were observed by IR analysis. The glass transition temperature of TLCP (<20 nm) in silica surface increased about 20^。C higher than that in bulk.